Preparation, characterization and application of a stationary chromatographic phase from a new (+)-tartaric acid derivative

The preparation, characterization and application of a new stationary phase derived from 1,4-cyclohexanedione and diethyl (+)-tartrate are described. A suitable TADDOL for immobilization has been synthesized and grafted to a γ-mercaptopropylsilylated silica gel. The resulting modified stationary phase has been characterized and its ability to separate enantiomers has been studied. While the free TADDOL in solution was able to resolve a range of enantiomers, the resolving properties were lost on immobilization. Solid state ¹³C CPMAS NMR of the new stationary phase was used to explain the lack of stereoselective recognition.     

Self-trapping of magnon Bose-Einstein condensates in the ground state and on excited levels: from harmonic to box confinement

Long-lived coherent spin precession of (3)He-B at low temperatures around 0.2T(c) is a manifestation of Bose-Einstein condensation of spin-wave excitations or magnons in a magnetic trap which is formed by the order-parameter texture and can be manipulated experimentally. When the number of magnons increases, the orbital texture reorients under the influence of the spin-orbit interaction and the profile of the trap gradually changes from harmonic to a square well, with walls almost impenetrable to magnons. This is the first experimental example of Bose condensation in a box. By selective rf pumping the trap can be populated with a ground-state condensate or one at any of the excited energy levels. In the latter case the ground state is simultaneously populated by relaxation from the exited level, forming a system of two coexisting condensates.     

Spin-asymmetric Josephson effect

We propose that with ultracold Fermi gases one can realize a spin-asymmetric Josephson effect in which the two spin components of a Cooper pair are driven asymmetrically--corresponding to driving a Josephson junction of two superconductors with different voltages V(↑) and V(↓) for spin up and down electrons, respectively. We predict that the spin up and down components oscillate at the same frequency but with different amplitudes. Furthermore our results reveal that the standard interpretation of the Josephson supercurrent in terms of coherent bosonic pair tunneling is insufficient. We provide an intuitive interpretation of the Josephson supercurrent as interference in Rabi oscillations of pairs and single particles, the latter causing the asymmetry.     

Superfluid vortex front at T→0: decoupling from the reference frame

Steady-state turbulent motion is created in superfluid (3)He-B at low temperatures in the form of a turbulent vortex front, which moves axially along a rotating cylindrical container of (3)He-B and replaces vortex-free flow with vortex lines at constant density. We present the first measurements on the thermal signal from dissipation as a function of time, recorded at 0.2T(c) during the front motion, which is monitored using NMR techniques. Both the measurements and the numerical calculations of the vortex dynamics show that at low temperatures the density of the propagating vortices falls well below the equilibrium value, i.e., the superfluid rotates at a smaller angular velocity than the container. This is the first evidence for the decoupling of the superfluid from the container reference frame in the zero-temperature limit.     

Waste mixture composition by thermogravimetric analysis

In this work thermogravimetric analysis is applied to examine pyrolysis of single waste components and their blends in order to determine the composition of an unknown waste mixture. The superposition property is assumed, i.e. the mixture thermal degradation curve is obtained as the sum of the curves corresponding to its constituents. The results show that if blended, the individual components are more clearly recognised from the differential mass loss curves. This allows a better identification of the composition. Inaccuracy in determining the composition increases if interactions occur between components, which is the case for PVC-newspaper blend. This revised version was published online in July 2006 with corrections to the Cover Date.     

Noncovalent attachment of pyro-pheophorbide a to a carbon nanotube

Pyrene mediated noncovalent attachment of a chlorophyll derivative, pyro-pheophorbide a, to a soluble single wall carbon nanotube is reported and the resultant CD, UV-Vis absorbance, fluorescence and 1H NMR spectra are discussed.     

Nanometer-scale displacement sensing using self-mixing interferometry with a correlation-based signal processing technique

A self-mixing interferometer is proposed to measure nanometre-scale optical path length changes in the interferometer’s external cavity. As light source, the developed technique uses a blue emitting GaN laser diode. An external reflector, a silicon mirror, driven by a piezo nanopositioner is used to produce an interference signal which is detected with the monitor photodiode of the laser diode. Changing the optical path length of the external cavity introduces a phase difference to the interference signal. This phase difference is detected using a signal processing algorithm based on Pearson’s correlation coefficient and cubic spline interpolation techniques. The results show that the average deviation between the measured and actual displacements of the silicon mirror is 3.1 nm in the 0–110 nm displacement range. Moreover, the measured displacements follow linearly the actual displacement of the silicon mirror. Finally, the paper considers the effects produced by the temperature and current stability of the laser diode as well as dispersion effects in the external cavity of the interferometer. These reduce the sensor’s measurement accuracy especially in long-term measurements.     

New high-energy luminescence bands from Co2+ in ZnSe

Three sharp absorption features in the energy range 2.36–2.55 eV have been detected in the transmission spectrum of Co-diffused ZnSe, and a number of luminescence transitions originating from the lowest of these states at 2.361 eV have been observed. Photoluminescence excitation spectra prove that these are high energy excited states of the Co²⁺_Zn impurity, a conclusion confirmed by comparison of measured and predicted luminescence energies. This represents the first identification of luminescence branching from a higher excited state of a transition metal ion in any semiconductor. The sharp, weakly phonon-coupled transitions involve either intra-impurity excitation or transitions from the impurity to localised states split off from a minimum in the conduction band. The implications of these observations for the mechanism of host-impurity energy transfer and for the nature of the excited state wavefunctions are discussed.     

Molecular hydrogen tweezers: structure and mechanisms by neutron diffraction, NMR, and deuterium labeling studies in solid and solution

The mechanism of reversible hydrogen activation by ansa-aminoboranes, 1-N-TMPH-CH(2)-2-[HB(C(6)F(5))(2)]C(6)H(4) (NHHB), was studied by neutron diffraction and thermogravimetric mass-spectroscopic experiments in the solid state as well as with NMR and FT-IR spectroscopy in solution. The structure of the ansa-ammonium borate NHHB was determined by neutron scattering, revealing a short N-H···H-B dihydrogen bond of 1.67 ?. Moreover, this intramolecular H-H distance was determined in solution to be also 1.6-1.8 ? by (1)H NMR spectroscopic T(1) relaxation and 1D NOE measurements. The X-ray B-H and N-H distances deviated from the neutron and the calculated values. The dynamic nature of the molecular tweezers in solution was additionally studied by multinuclear and variable-temperature NMR spectroscopy. We synthesized stable, individual isotopic isomers NDDB, NHDB, and NDHB. NMR measurements revealed a primary isotope effect in the chemical shift difference (p)Δ(1)H(D) = δ(NH) - δ(ND) (0.56 ppm), and hence supported dihydrogen bonding. The NMR studies gave strong evidence that the structure of NHHB in solution is similar to that in the solid state. This is corroborated by IR studies providing clear evidence for the dynamic nature of the intramolecular dihydrogen bonding at room temperature. Interestingly, no kinetic isotope effect was detected for the activation of deuterium hydride by the ansa-aminoborane NB. Theoretical calculations attribute this to an "early transition state". Moreover, 2D NOESY NMR measurements support fast intermolecular proton exchange in aprotic CD(2)Cl(2) and C(6)D(6).